Boebel Timothy A, Hartwig John F
Department of Chemistry, University of Illinois, Urbana, Illinois 61801, USA.
J Am Chem Soc. 2008 Jun 18;130(24):7534-5. doi: 10.1021/ja8015878. Epub 2008 May 22.
The regioselectivity of the borylation of arenes catalyzed by the combination of 4,4'-di-tert-butylbipyridine (dtbpy) and [Ir(cod)Cl]2 has typically been governed by steric effects. We describe a strategy that makes use of a new substituent for ortho-functionalization to overcome this bias. We show that arenes containing hydrosilyl substituents on an atom attached to the arene ring undergo borylation at the position ortho to the hydrosilyl group. Using iridium-catalyzed formation of silyl ethers and silylamines from silanes and either phenols or arylamines, we have developed the ortho-borylation into a one-pot conversion of free phenols and monoprotected anilines into hydroxy- and amino-substituted organoboron derivatives.
由4,4'-二叔丁基联吡啶（dtbpy）和[Ir(cod)Cl]₂组合催化的芳烃硼氢化反应的区域选择性通常受空间效应控制。我们描述了一种利用新的取代基进行邻位官能化的策略来克服这种偏向。我们表明，在与芳环相连的原子上含有氢硅烷基取代基的芳烃在氢硅烷基的邻位发生硼氢化反应。通过铱催化由硅烷与酚类或芳基胺形成硅醚和硅胺，我们已将邻位硼氢化反应发展成为一种将游离酚和单保护苯胺一锅转化为羟基和氨基取代的有机硼衍生物的反应。
